Water-insoluble monoazo dyestuffs



WATER-INSOLUBLE MONOAZO DYESTUFF S Ernest Merian, Bottmingen, near Basel, Bruno J. R. Nicolaus, Basel, and Walter Wehrli, Riehen, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a SWISS firm No Drawing. Application April 22, 1957 Serial No. 654,078

Claims priority, application Switzerland April 27, 1956 7 Claims. (Cl. 260-207) The present invention relates to new water-insoluble monoazo dyestufis which correspond to the general formula wherein:

and the nucleus A may be further substituted by nonionic substitutents.

The process for the production. of the new waterinsoluble monoazo dyestuffs consists in reacting a monoazo dyestufi of the general formula meanings,

wherein A, R and x have the above-defined meanings with 1 mol of a chloroformic acid ester.

The alkyl, cycloalkyl, aralkyl or aryl radical denoted by R in Formula I may more specifically represent a branched or an unbranched alkyl radical with l to 6 carbon atoms and which may contain hydroxy groups, ether groups and/or secondary amino groups, an alkyl radical substituted by aryl, aryloxy or a hetero-ring and having in all not more than 11 carbon atoms, or a phenyl radical which may be substituted by halogen atoms and/ or methyl, methoxy, ethoxy, dimethylamino or diethylamino groups.

The nucleus A may within the present definition contain further substituents as for example hydroxy, methyl, ethyl, methoxy, ethoxy, alkylsulfonyl and/or alkylaminosulfonyl groups.

When the radical represented by R in Formula I stands for a carboxylic acid acyl radical, it may be the radical of acetyl, propionyl, butyryl, isobutyryl, methoxy- 2,870,137 Patented Jan. 20, 1959 acetyl, ethoxyacetyl, 2-methox'ypropionyl, 2-ethoxypropionyl, 3-methoxybutyryl, 3-ethoxybutyryl or benzoyl. When it stands for a lower alkyl radical it may be the radical of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or 2-cyanoethyl.

The aminomonoazo Compounds 111 used as starting materials in the second operating procedure of the process can be obtained, for example, by the reduction of nitro compounds of the general formula wherein A, R; and x have the aforenamed meanings,

or by coupling the diazo compound of 4-amino-l-hydroxybenzene derivatives etherified or esterified on the hydroxy group and having the general formula wherein R and x have the aforenamed meanings,

with aminobenz ene derivatives of the general formula wherein A has the aforenamed meaning. The reaction of the monoazo dyestuif (II) with the acylating or alkylating agents according to the first op erating procedure and the reaction of the aminomonoazo Compound III with the chloroformic acid esters according to the second operating procedure of the process are conducted advantageously in solution (for example in an indilierent organic solvent) or in a very fine aqueous suspension or solution, preferably in the presence of a proton acceptor. The reaction temperature can vary within wide limits according to the procedure adopted.

The dyestuiis are isolated by one of the sta'ndard basic operations such as filtration, evaporation of the solvent or precipitation from the solvent with a suitable agent.

The new water-insoluble monoazo dyestuffs dye cellulose ester fibers,.e. g. acetate and triacetate, polyvinyl fibers, synthetic polyamide fibers, e. g. nylon, Perlon (registered trade name) and terephthalic acid. ester fibers, e. g. Terylene', Dacron yellow to orange shades. They possess a good affinity for these fibers from aqueous suspensions, preferably in the presence of compounds with dispersing action and at elevated temperature. In some instances the affinity can be further improved by using mixtures of two or more dyestulis of the general Formula I. Certain of them are also well suited for dyeing spinning solutions of cellulose acetate, cellulose triacetate, polyvinyl and polyacrylonitrile. The dyeings obtained from aqueous suspensions as well as the spun filaments dyed in the dope are dischargeable and possess excellent iastness to light, washing and chlorine in alkaline and, in some instances, in acid medium. They show also good fastness to alkali, acids, sublimation, cross-dyeing, perspiration, gas fumes and peroxide bleaching. Certain of the new dyestuffs are suitable for coloring lac- (registered trade names) in a n3 quers oils and synthetic resins. A number of them also dye wool, silk and polyacrylonitrile fibers, e. g. Dynel, Orlon, Acrilan (registered trade names).

The water-insoluble monoazo dyestufls which are particularly suitable for dyeing cellulose acetate from aqueous suspension or in the spinning solution correspond to the general formula 4, completed. The goods are removed, rinsed and dried. In order to improve the dispersion the dyestuff can be previously ground with suitable wetting, dispersing or emulsifying agents, preferably in the presence of an inorganic salt such as Glaubers salt. Alternatively, an aqueous paste of the dyestuff can be prepared and intimately mixed with a dispersing agent; the mixture then being suitably dried to give a dyestutt powder.v

NH-OC-R6 f 6 EXAMPLE 2 H(l3 (CH2)H-O O 4 RB 40 parts of 1-(2'-acetylamino-4'-hydroxy)-phenylazo- (VII) phenyl-4-carbamic acid-3"-methoxy) -butyl ester (meltwherein: ing point 208209) are finely pulverized and dissolved in a solution of 12 parts of sodium hydroxide in 200 Rsai lgr lftreasdlgtllrogen or alower branched or unbranched parts of Water at 10409 14 p t of dimethyl SUL R denotes hydrogen, hydroxy, alkoxy, dialkylamino or i are added 9 F 3 5 in three portifims a lower alkyl radical;- with thorough stirring. After some time the reaction R denotes an alkyl radical containing from 1 to 4 car- 15 l" l r ee te d- W -ml? l 0E; hon atoms, h lt Pe a W s ed-g mmermele t ma-PH R denotes an alkanoyl radical --containing between 2 value of i 3 yield is obtained and 4 carbon atoms or a methyl, ethyl or hydroxy of the resulting l-(2 -acetylamin t 4 -rnethoxy)-phenylethyl radial" nd 1 azo-phenyl- 4 carbamic acld- (3 -methoxy)-butylester. n stands for bf'the integers 1, 2, 3 4,5 and, 6 The new product crystalhzesout from alcohol as bright yellow needles with a melting po nt at l47-148. It n the fellewlng examples all Parts e PFYCentages dissolves in acetic ester with a greenish yellow coloraare y welght; the mp e are glven 111 degrees tion and in sulfuric acid with an orange coloration. centlgrade a1'ldthe meltlflg P01nts are uneol'fecled- The dyestutf dyes cellulose acetate and triacetate and polyamidefibers in yellow shades of excellent fastnes s LE" to Washing and seawater. The 'dyeings are discharge 40 parts of l-(2'-acetylamino4'-hydroxy)-phenylazo- 39 able, fast to sublimation, gas fumes, peroxide bleachphenyl-4- carbamic acid-(3" methoxy) -butyl ester ing and chlorine bleaching, and very fast to light: The (melting point 208-209?) are. finely pulverized and dis- Solubility of the new monoazo 'dyestufiin acetone is 100 solved in 200 parts of pure pyridine with exclusion of gm. per liter. moisture. 9. parts of acetyl chloride are added drop- Other alltylating agents, e. g. the. benzene=or i methwise to the reaction mass at 10 with vigorous stirring. ylbenzene-l-sulfonic acid alkyl esters, and. the alkyl Stirring is continued for 2 hours at room temperature al de-safe also Well suited for use in'the,process. and for a further 4 h urs t 75 100 parts. of cellulose acetate are run. into. 300 parts At this point the mixture is acidified. The precipif l n ne ne ltf e a tated dyestuff is filtered ofi and the filter cake washed ort ime and left overnight to swell. ()5 part of the with water until it shows a pH value of 7, whereupon 40 dyestufi 0f the Present eXHmPIe is dissolved in 85 Parts it is dried. A good yield is obtainedgof the resulting of the solvent y simple agitation, the solution then 1 (2' acetylamino 4 acetoxy) phenylazo- 'phenbeing added to the cellulose acetate solution. The spinyl-4-carbamie acid-(3"-methoxy)-buty1 t Th w ning solutionthus obtained is stirred in an open vessel product crystallizes out from alcohol'in the form of A5 11115160 Parts Of the Solvent Y evaporated- The y beautiful red needles with a melting point at.132-133. ss s pumped into the spinning machine and spun in It dissolves in acetic esterwith a greenish yellow colorathe nerfnal y; the y m n is e yr for he tion and in sulfuric acid withgan orange coloration. The P gdyestuif dyes celluloseacetate, cellulose triacetate and 111 the fellowin'g- Tablev further Valuable dieliefee polyamidet fibers in yellow shadeszofexcellent fastness 59 dyestuffs aredeseflbedwhleh can be Producedbyone 0f ew hins nd awater. The dyeings. ar di char the procedures described above. They correspond to the able,. fast to sublimation, gas fumes, peroxidebleaching general formula and chlorine bleaching, and very .fast tolight. The solubility of this new monoazo. dyestufiin acetone is gm. per liter. 55 m-o-oo-nn- N=NR.-

A ye v p p red with 0.6 part of the dyestufi (VIII) obtained as described in the. first. section of the present example and dispersed withTurkey red oil, 6 parts of a The meanings of R R and y are recited in the approsulfonated fatty alcohol and 3000 parts of water. 100 priate columns; in another column the melting points are parts of cellulose acetate are immersed in the dyebath m noted; in the. penultimate. and final columns respectively at room temperature, which isv then heated to in the shades of the dyeingson cellulose acetate and the the course of 1' hour and held at this temperature for acetone-solubility of the. dyestuff in gm. per liter are a further hour. After this time the dyeing process is recorded.

Table I Shade of Solubility Ex. 1!. R1 R1 M. P., dyeing on inacctone, No. degrees cellulose gm per acetate lit-er Yellow-.. 65 fffi ififfiffff'iiii 3'Efili$$hi$$i$l 129 H 2-chloro-acetyl-4-u1ethoxyphcnyl 22 H 4-rnethoxy-phenyl l0 H 2-hydroxy-4'-methoxyphenyl 5 EXAMPLE 8 water. The solution is ice-cooled to 0 and drop-fed crystallizes out of ethanol in the form of small brownred sticks with a melting point at 117' and dyes cellulose acetate and polyamide fibers in bright reddish yellow shades.

Y he 0 ow" T bl I co tains further valuable water- Wllh a solution of parts of sodium nitrite m 100 parts 5 T f 11 mg a e I n f insoluble monoazo dyestuffs whlch are obtainable ac- 0 water. The resulting diazo solution is combined according to the details given 111 Examples 1, 2 or 8. They with parts of l-ammo-3-hydroxybenzene in 500 parts correspond to the general formula of water and 30 parts of acetic acid. After the'addltion of parts of sodium acetate the preclpltated 4-ethoxym O CHB 2-hydroxy-4-am1no-1.l'-azobenzene 1s filtered off. A dyestufi paste is obtained which is adjusted to 700 parts Rr-O-O O-HN N= O-Rz with water. Then 80 parts of sodium acetate 'and parts of sodium chloride are stirred in. 600 parts or Y 7 ice are added to give a freezing mixture, after which 15 and are characterized m the table by the symbols R 'R 70 parts of chloroformtc acid ethoxyethylester are added and y and by the shade of their dyemgs on cellulose slowly. The new dyestufi 1s filtered ofi and dried, It acetate.

Table 11 Shade of BL y R; R: dyeing on No. cellulose acetate Z-methoxyethyl Methyl Yellow. 2-ethoxyethy1 Do. 3-methoxypropyL. Do. Z-metboxypropyL- Do. 2-ethoxypropyl. Do. 4-methoxybutyL Do. 2-methoxyethyl- Do. 2-ethoxyethyl--. Do. 3-methoxybutyl Do. ..-do Do. Do. D0. Do. Do. Do. Do. Do. Do. xypropionyl D0. xybutyryl. Do. Ethoxyacetyl Do. MethoxyacetyL. Do. 3-methoxybutyryl. Do. 2-methoxyprop1onyl. Do. Methyl Do. do do Do. 4-metl1ylphenyl Do. 3-methoxyphenyl Do. 4-ethoxyphenyl Do. 4-dlmethylamlnophenyl- Do. d-diethylaminophenyl Do. 2-morpholylethyl Do. 2-phenoxyethyL. Do. 2-phenylethyl- Do. Benzyl Do. 2-hydroxyethyL- Do. 3-hydroxypropyl Do. Z-dimethylamlnoethyL... Do. Zdlethylaminoeth Do. 3-methoxybuty1 Do. do Do. y do Do. 61 Z-methylsulfonyl do Do. 52 2-methylamlnodn Do.

f0 yl D0. Do. Do. Do. D0. Do. Do. Do. Do. 2-aminosulfonyl.- Do. Z-ethylamlnosul- Do. fonyl. l 2-(2-hydroxy)-eth- Do.

ylaminosulfonyl. 2-(3'-methoxy)-pro- Do.

tiylaminosuldo 4-methylbenzoyl Do. r'in 4-chlorobenzoyl..... Do. do Methyl Do. Isopropyl .-do....-' Do. n-Butyl do Do.

n-Propyl do I Do.

Im bcs ollowi x Ta l I- aretenume atc watern: p y yp yhi hox phe y methylsulfonylol bl mo oazo ye tuffs ob a nable. cord g to the, ph nyb. et y o ph ny y v q n tulfony deta ls ieni heExarnp Q1; 2m hey...9 .e.-' P y newsworthin s d yhi iyh iitc hf ixi i i spond to the Formula VIII and are characterized in the pylaminosulfonylphenyl and aniiniis'iilffir'iylphehfl? Phi table. by the symbol R1, han /mud, ye hesh sle of 5 'b ents *aI e i el froth the 1 the V y inss on cel lose a etate.

Shade of Ex. :1 R1 R; dyeing on No cellulose acetate 2-proptonylamino-'acetoxyphenyl- Yellow.

phenyl. g n-Butyl 2'-acatylamlno-4'4netboxyphenyl. I Do. 2-ethoxyethyl. 2 115013101113!amlno-4'-mel:hoxy- Do.

p any 3 -methoxyprop vl -d0 Do. B-methoxybntyl 2-methoxy--l-aeetoxyphenyl Do. undo 2-ethoxy-4-methoxyphenyl e Do. 2',4-dimeth0xyphenyl Do. 2-methyl-a-mathoxyphenyl Do. 2"ethyl-4'-meth0xyphenyl Do.

oxyphenyl.

3-rnethyl-4-methoxyphenyl Do.

2-isovalerylamlno-4-methoxyphenyl Dot do do Do. 91 H 3-mcthoxybutyl-.. .-...do Do.

Iiepresentative dyestufis the foregoing examples mejthoir jphenyl, ethoxyphenyl, alkanoylaminophenyl concorrespond to the formulae taining'less than 6 carbon atoms in the alkanoyl group, I EXAMPLE 1 and alhylsulfonylaminophenyl containing less than 5 NH-0OCH CH3 'I" HsC-OH(3-H:G -HzCO-CO -HNC -N;N -OOGOH;

EXAMPL NH-O C-CH; CH 7 EXAMPLE 3 t ETQ Q A CB* CHa EXAMPLE 8 carbon atoms in the alkyl group, R represents a memo ber' selected from the group consisting of alkyl contain- V 5 5 mg less than 9 carbon atoms, hydroxyalkyl containing HSCTOJLCTWCoflmglqmomomsV less than 4 carbon atoms, alkoxyalkyl containing alto in gether lelss than 6 carbon atoms, dimethylaminoethyl,

' mononuc ear aryl, mononuclear aryloxyethyl, morpholyl- EXAMPLE 10 ethyl, benzyl and phenylethyl, and R represents a mem- T' (343113 ber selected from the group consisting of cyanoethyl,

alkyl containing less than 5 carbon atoms, alkanoyl coniC2- 'O O taining less than 5 carbon atoms, alkoxyalkanoyl containin'g less than 7 carbon atoms and mononuclear aryl- EXAMPLE 77 carbonyl, and wherein the groups R -OCO-HN- NE-Q C-QHa-Cfi 455 and,-O R are in para-position to the N=N group. p j 2. Afwater-insoluble monoazo dyestuff which corre- H;C Q-,HCr0-QQHN =N J H sponds to the formula Having thus disclosed the invention what is claimed is:

I I 1. A water-insoluble monoazo dyestuflf which come T C O sponds to the formula wherein Ph represents a membertselected ifromjhe group 7; represents an alkanoylarnino radical containing less than consisting of phenyl, hydroxyphenyl,methylphenyl,.ethy1-. .75 5. c'arbon atoms,

, 2,870,137 9 3% R represents an alkoxyalkyl radical containing alto- 7. The water-insoluble monoazo dyestufi which corregether less than 6 carbon atoms, and sponds to the formula R represents an akyl radical containing less than 5 car- NH-OC-CHg-OHa bon atoms. 3. The water-insoluble monoazo dyestufi which corre- 5 H5Cz-OH4C2-O-C O-HNO =NO0-cm sponds to the formula 4. The water-insoluble monoazo dyestufi which corresponds to the formula NIH-O C-CHz-CHa CH;

5. The water-insoluble monoazo dyestufi which corre sponds to the formula 1 NH-O C-CHPCHT'CHS CH3 References Cited in the file of this patent UNITED STATES PATENTS 6. The water-insoluble monoazo dyestufl which corresponds to the formula NH OC OH3 1,735,960 Dreyfus Nov. 19, 1929 35 FOREIGN PATENTS O O'CHB 879,986 France Dec, 10, 1942 

1. A WATER-INSOLUBLE MONOAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 